| Summary: | 碩士 === 大同大學 === 化學工程學系(所) === 99 === PART 1
In the first part the abstract as follows. Bis[4-(phenyl-isopropyl)phenyl]-4-nitrophenylamine (PNPA) (iii) was firstly synthesized by nucleophilic substitution of 4-fluoronitrobenzene (ii) and bis-[4-(phenyl-isopropyl)phenyl]amine (PA) (i) in this study, and then PNPA (iii) was reduced to bis[4-(phenyl-isopropyl)phenyl]-4-aminophenylamine (PAmPA) (iv). At last, acrylation of PAmPA (iv) with acryloyl chloride was performed to obtain the bis[4-(phenyl-isopropyl)phenyl]-4-acrylamidophenylamine (PAcPA) (v). Then, a series of thermosensitive hydrogels were prepared by copolymerization of PAcPA and N-isopropyl acrylamide (NIPAAm) by UV irradiation. The effect of PAcPA content in the copolymeric hydrogels on the swelling ratio, mechanical properties, and drug release behaviors of the gels was investigated. Results showed that the swelling ratios of the copolymeric hydrogels decreased from 8.2 (g/g) to 5.01 (g/g) when the hydrophobic monomer PAcPA content in the copolymeric gel increased from 0.1 mol% to 0.9 mol% due to the decreasing hydrophilicity. In addition, the thermosensitive behavior obviously decreased with increasing of PAcPA content in the hydrogels, but the mechanical properties and crosslinking density of the hydrogel increased with increasing of PAcPA content; the caffeine drug release ratio decreased from 46% to 29%. The result of drug release also showed when the the the content of PAcPA in the hydrogel increased, the drug-loadings of the hydrogel decreased, but fractional release increased. In addition, the corresponding copolymers of the copolymeric hydrogels were prepared by the free radical polymerization. Furthermore, the PAcPA monomer was dissolved in DMSO with different concentrations, the NIPAAm/PAcPA hydrogel and NIPAAm/PAcPA copolymer were respectively swollen and dissolved in some solvents with different polarities, and then separately measured their maximum wavelengths of UV absorbance and PL emission.. The results showed the luminescence intensity increased with increasing PAcPA amounts, especially the wavelength had obvious blue shift phenomenon in THF solvent. The wavelength of UV absorbance and PL emission of PAcPA all appeared in visible region. No matter what monomer, NIPAAm/PAcPA hydrogel or NIPAAm/PAcPA copolymer, the wavelengths of UV absorbance and PL emission in DMSO solvent are all the same.
PART 2
In the second part, bis[4-(phenyl-isopropyl)phenyl]-4-cyanophenyl amine (vi) (PCyPA) was firstly synthesized by nucleophilic substitution of 4-fluoro-benzonitrile (ii)’ and bis[4-(phenyl-isopropyl)phenyl]-4-phenyl amine (PA) (i) in this study. Then, the hydrolysis and acidification of the PCyPA (vi) was performed to obtain bis[4-(phenyl-isopro-pyl)phenyl]
-4-carboxy-phenylamine (PCaPA) (vii), and then esterification with HEMA to obtain methacryloyloxy ethylene-oxy-carbonyl bis-[4-(phenyl-isopropyl)phenyl]amine (MEOPA) (viii). Then, a series of thermosensitive hydrogels were prepared by copolymerization of MEOPA and N-isopropyl acrylamide (NIPAAm) by UV irradiation. The effect of MEOPA content on the swelling ratio, mechanical properties of the hydrogels was investigated. Results showed that when the hydrophobic monomer MEOPA content in the copolymeric hydrogel increased from 0.1 mol% to 0.9 mol%, the swelling ratios of the copolymeric gels decreased from 4.73 (g/g) to 1.74 (g/g); the gel strength and crosslinking density increased with increasing the MEOPA monomer amounts. In addition, the release ratio of caffeine also decreased from 70% to 25%. In photoluminescent behavior, the intensity of photoluminescent increased with an increase of the content of MEOPA in the copolymeric hydrogel. On the other hand, the corresponding copolymers of copolymeric hydrogels were prepared by the free radical polymerization.
Furthermore, the MEOPA monomer was dissolved in DMSO with different concentrations, the NIPAAm/MEOPA hydrogel and NIPAAm/ MEOPA copolymer were respectively swollen and dissolved in some solvents with different polarities, and then separately measured their maximum wavelengths of UV absorbance and PL emission.. The results showed the luminescence intensity increased with increasing MEOPA amounts. especially the wavelength had blue shift phenomenon in THF solvent. The wavelength of UV absorbance and PL emission of MEOPA appeared in invisible and visible region respectively. No matter what MEOPA monomer, NIPAAm/MEOPA copolymer or NIPAAm/MEOPA hydrogel, their wavelengths of UV absorbance and PL emission in DMSO are all the same.
PART 3
In the third part, 1-nitropyrene (1) was firstly synthesized by pyrene and copper(II) nitrate in this study, and then compound (1) was reduced to 1-aminopyrene (2). At last, acrylation of compound (2) with acryloyl chloride was carried out to obtain 1-acrylamidopyrene (3) (AAP). Then, a series of thermosensitive hydrogels were prepared by copolymerization of AAP and N-isopropyl acrylamide (NIPAAm) by UV irradiation. The effect of AAP content in the copolymeric gels on the swelling ratio, mechanical properties, and drug release behaviors of the hydrogels was investigated. Results showed that the swelling ratios of the copolymeric gels decreased from 6.5(g/g) to 4.9 (g/g) when the hydrophobic monomer AAP content in the copolymeric hydrogel increased from 0.1 mol% to 0.9 mol% due to the decreasing hydrophilicity. In addition, the thermosensitive behavior obviously decreased with increasing of AAP content in the gels, but the mechanical properties and crosslinking density of the hydrogel swollen in the ethanol solution increased with an increase of AAP content. The swelling ratios of hydrogels were changed by increasing AAP content in the different solvents. The result of drug release showed that when the content of AAP in the hydrogel increased, the caffeine-loading in the hydrogel decreased but the fractional release increased. In addition, the corresponding copolymers of NIPAAm/AAP copolymeric hydrogels were synthesized.
Furthermore, the AAP monomer was dissolved in DMSO with different concentrations, the NIPAAm/AAP hydrogel and NIPAAm/AAP copolymer were respectively swollen and dissolved in some solvents with different polarities, and then separately measured their maximum wavelengths of UV absorbance and PL emission..The results showed the luminescence intensity increased with increasing AAP amounts. especially the wavelength had blue shift phenomenon in THF solvent. The wavelength of UV absorbance and PL emission of AAP all appeared two absorption peaks. The wavelength of UV absorbance of AAP appeared in invisible region, and major PL emission peak of AAP appeared in invisible and minor peak in visible region. No matter what AAP monomer, NIPAAm/AAP copolymer or NIPAAm/AAP hydrogel, their wavelengths of UV absorbance and PL emission in DMSO are all the same.
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